Polypropylene benzene sulfonate



latented 27, 1953 orrlcs POLYPROPYLENE BENZENE SULFONATE DETERGENTCOMPOSITIONS CON- TAINING TETRASODIUM PYROPHQS- PHATE Samuel A. Russell,III, Chicago, 111., assignor to Allied Chemical-d: Dye Corporation, NewYork, N. Y., a corporation of New York No Drawing. Application January29, 1949,

. Serial No. 73559 3 Claims. (cuss-13s) This invention relates to themanufacture of detergent compositions. It is particularly'concemed withimprovements in detergent compositions of the alkyl benzene 'sulfonatetype.

The manufacture of alkyl benzene sulfonate detergents normally involvesalkylation of benzene, sulfonation of the alkylatedbenzene, andneutralization of the sulfonic acid product. Neutralized productsobtained in this manner may be used without further treatment or withonly removal of water, and in this condition are effective and eiiicientdetergent compositions. Such compositions normally contain between 30%and,45% of alkyl benzene sodium sulfonate, and between 55% and 70% ofsodiumsulfate. In some cases the mixtures are treated for removal of thesodium sulfate to roduce alkyl benzene sodium sulfonates substantiallyfree of inorganic salts.

For the manufacture of detergents of the above types benzene has beenalkylated by several methods and by several types of" alkylatingcompounds. For example, benzene has been condensed with chlorinatedkerosene fractions in the presence of an aluminum chloride condensingagent. Benzene has been condensed also with. oleflns from varioussourcesfer'nploying aluminum chloride, sulfuric acid, or other suitablecondensing agent. Olefln's employed for this alkyli tion have beenobtained by dehydration of alcohols, by cracking of'petroleum products,and by polymerization processes. Thus oleiins obtained bypolymerizationof propylene, butylenefisobutylene and amylene have beenproposed:

Regardless of the source. the most suitable alkylating compounds arethose providing alkyl groups containing between 9 and 18 carbon atoms.

'Alkyl benzene sulfonate detergents have been marketed alone andalso inadmixture with other detergent materials, among which may be mentionedthe phosphates, such as trisodium phosphate and sodium triphosphate.-Experimental tests have demonstrated that while'such phosphates mayimprove some commercial alkyl-aromatic sulfonate detergents slightly,the immovement is not great. Moreover, tetrasodium pyrophosphate doesnot always promote the detergent action of such alkyl benzenesulionates.

as illustrated by its effect, in a normal hard I water, upon acommercially available detergent comprising alkyl benzene sulfonatesderived from chlorinated kerosene and upon such; a detergent derivedfrom polypropylene fractions having an average molecular carbon"content-"of 12 carbon atoms, as shown in Table 11 below.

- a decidedly "beneficial effect upon polypro' pylene benzene sulfonatedetergents having an average of 13 to 15 carbon atoms in thepolypropylene radicals and containing a substantial proportion ofpentamers among 'the "polypropylene radicals. This discovery has ,led tothe production of superior detergent compositions and furthermore haspermitted utilizing for the production of such compositions.substantially less expensive starting-materials.

The compositions of my invention comprise such "polypropylene"benzenesodium sulfonates in which the "polypropylene radicals contain anaverage of 13 to 15 carbon atoms, and in addition to the sulfonate.between 1 and -3 parts of sodium sulfate and between 1 and [4 parts oftetrasodium pyrophosphate for 'each part by weight of the sulfonate,these proportionsbeing determined on the dry basis. The products'of theinvention when employed inwater atfaconcentration of 54% provide a pHbetween 19 and 10.4.

Polypropylene fractions of ab0ut2 00 to -2'70" C. boiling range boilingfor the most part between-210 and 260 C. have the required averagemolecular carbon content and contain penta- .propylenes as the majorcomponent. 'Such polypropylene fractions. suitable forpreparingiheproducts of the invention, are available commercially. They are'normally produced by the superatmospheric poLvmerization of propylene1'12 parts of 95% msoi is mixed with 42 parts of benzeneat 10 to 20 C.65 parts of polypropylene, distilling at normal atmospheric presthemixture is stirred for 1% hours at a temperature not above 30' C. Theproduct is then woven cotton fabric soiled with a suspension of graphitein lubricating oil and cottonseed oil. The proportion of soil removedwas determined photometrically.

- when the above detergents were mixed with tetrasodium pyrophosphateand tested at a total detergent concentration of 0.25%, employing anidentical test, substantially diflerent results were allowed to stratifyand the heavy H2504 layer is obtained. The following table shows thevariawithdrawn. The alkylate which remains is hell-' tion of "theseresults with varying proportions of tralized with aqueous sodiumcarbonate solution; pyrophosphate.

,racliz -;1?etes'gentTBPP Ratio Dem- 1'' 00-10 ao-ao vo-ao 00-40 50-5040-00 Pol pylons (Cu) Benzene Bodiunr 1 I 8 cute Detergent (62% No.80 i722 2Q 30 48 51 44 Pol pylene (Cu) Benuno Sodium 1 ..B ionataDet rst(62%Nu80|).. .40 N 33 34 'Keryl Benzene Sodium flulionate 1 DOm (a% N284)----' as so as as as as an stripped with steam to. remove bnreactedbenzene... After removal ofthe benzene the ,alkylate is againpermittedto stratify muse water andsodium' sulfate and sodiumcarbonateare drawn The remaining, alkylate isthenj driedanhydrouscalciunrchloride and separated fromthis drying agent. i

' Toeflect sulionatiori ,oithe alkylate 50 parts of si lete is cooled tobetween l0'fi-and c.

an 190 parts off 20% oleum is added w llie the mixture is s i r vis musv w t ca in to maintain the temperature below 20' C. when-all ofi'th'eoleum has been added. ag'ii'ntior is conunseat until the end of 4hoursif'rorn the tin e of starting the addition of oleum, thetemperature being maintained during this period below CI 1' Thesulfonation mixture is then'int'roduced gradually into 285 parts of-aque'ous 25%- NaOH'liolution at a temperature of about -C.

The" pH of the slurry is adjusted finally to ap'-' proximately '7 by theaddition of sulfuric acid and the/slurry is then dried. Drying may beeflected by means of a drum drier or a spray drier at 110 C. The dryproduct contains about 38% of alkyl benzene-sodium sulfonate and 62% ofsodium sulfate. Upon application of the'pr'ocess oha' large scale. thecontent'of alkyl benzene sodium sulfonatel and sodium sulfate may vary5%; above'or below these values.

, Arne. following tables show the results of,

launderometer' tests 'of this detergentIpmduct-incomparison with" acommercial product made from chlorinated 'kerosene and a: polypropylenebenzene s'ulfonate having'an'average of-only 12 efirbonatoms 'in thepolypropylene? radicals. Thesertests were made employingha'vlng ahardness corresponding -to 300 parts per million of calcium carbonate.

Table! Pol ro ylene Be an; 8111- t IBen. innate Detergent Goneentration,Percent a acne B ul flie values in thistable represent' the percentageremoval than the'b'ir polypropylene benzene sulfon'ate deterde'ntjbutuponladd'itionjof tetra- W"! -PYIPPK SR 'FE. gave p0prer, and... poorerresults, and'in nepase gave better results than -the 'ab ence of thei'etrssodi m ymphosphate. ereas It ac poly op ene ul m t upon additionof e r -s di m p rop bhete s better, and better results; until .at a59-60 ratio this detergentl'was substantially. superior to any of themixtures of keryl benzene sulf onate. as'well as to this product withoutthe tetrasodium pyro phosphate. The product from 12 carbon atom(average) polypropylene .resembled the keryl product in its behavior andall its mixtures with 'I'SPPtested were inferior tothe 100% detergentproduct. l

I claim: 1

.1. A detergent composition consisting essentlally; of "polypropylenebenzene sodium -.sulfonate, in .which the polypropylene radicals convtain anaverage of between 13 and 15 carbon atoms and comprise asubstantial proportion of pentapropylene" radicals, and for about. each'one part by, weight ofpolypropylenebenzene so-- dium sulfonate. (drybasis), between 1 and 3 parts. of sodium sulfate and between 5 -and,.4-.parts.of t'etrasodiurn pyrophosphate. I

2. A detergent composition consisting. essential: ly of "polypropylene?benzene sodiumsulfonate, in which the polypropyleno radicals correspondsubstantially entirelyto. olefins boiling between 200 anda270 0.,comprise as the major com ponent-pentapropylene radicals and contain anaverageof between-13 and 15 carbon atoms; and for about each one part byweight of polypropylene benzene sodium sulfonate-(dry basis), .-be-,tweenf1.3, and 2'parts oi. sodium sulfate and between 1 and 8 partsf'oftetrasodium pyrophos pirate;

. 3. ll-detergent composition consisting'essential ly of polypropylene"--benzene sodium sulfonat'e'; in which the polypropylene" radicalscorrespond substantially entirely to oleilns boiling betweensdnwemdveain a standard inyolving a 200' and 270 d. and predominantlybetween 210 "pentapropylene radicals and contain an average of between13 and 15 carbon atoms, and for about each one part by weight ofpolypropylene benzene sodium sulfonate (dry basis) about 1 /10. parts ofsodium sulfate, and for each part of total sulfonate and sulfate aboutto 1 part of tetrasodium pyrophosphate.

SAMUEL A. RUSSELL, III.

REFERENCES CITED The following references are of record in the file ofthis patent:

6 UNITED STATES PATENTS Number Name Date Riegler Oct. 5, 1943 TrefiierJune 13, 1944 McGhie Feb. 5, 1946 Lind Mar. 12, 1946 Lewis July 26, 1949Lewis July 26, 1949 Strain Nov. 1, 1949 OTHER REFERENCES Oil and Soap,vol. 23, 1946, page 105.

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF "POLYPROPYLENE"BENZENE SODIUM SULFONATE, IN WHICH THE "POLYPROPYLENE" RADICALS CONTAINAN AVERAGE OF BETWEEN 13 AND 15 CARBON ATOMS AND COMPRISE A SUBSTANTIALPROPORTION OF "PENTAPROPYLENE" RADICALS, AND FOR ABOUT EACH ONE PART BYWEIGTH OF POLYPROPYLENE BENZENE SODIUM SULFONATE (DRY BASIS), BETWEEN 1AND 3 PARTS OF SODIUM SULFATE AND BETWEEN 1/3 AND 4 PARTS OF TETRASODIUMPYROPHOSPHATE.